CN109167099A - A kind of battery of high safety and preparation method thereof - Google Patents
A kind of battery of high safety and preparation method thereof Download PDFInfo
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- CN109167099A CN109167099A CN201811025261.3A CN201811025261A CN109167099A CN 109167099 A CN109167099 A CN 109167099A CN 201811025261 A CN201811025261 A CN 201811025261A CN 109167099 A CN109167099 A CN 109167099A
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- ptc
- pole piece
- collector
- battery
- tab
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/63—Control systems
- H01M10/637—Control systems characterised by the use of reversible temperature-sensitive devices, e.g. NTC, PTC or bimetal devices; characterised by control of the internal current flowing through the cells, e.g. by switching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides battery of a kind of high security and preparation method thereof, battery includes battery core shell and the battery core composition for being located at the battery core interior of shell；The battery core is made by PTC pole piece, anode pole piece, diaphragm, cathode pole piece and electrolyte assembling；The PTC pole piece includes collector A, PTC coating and collector B set gradually；A tab is equipped on the anode pole piece, cathode pole piece, collector A and collector B；The form of the assembling is lamination or winding；PTC pole piece is placed in the first layer and/or the last layer of lamination or places PTC pole piece in the innermost layer of winding and/or outermost layer, can effectively prevent the thermal runaway of battery, there are the security features such as good anti-overcharge, over-discharge, short circuit, improve the safety of battery.The battery structure is simple, easy to accomplish, it is easy to accomplish industrialization promotion.The present invention improves the safety of battery by the way that PTC pole piece is arranged in battery core.
Description
Technical field
The invention belongs to battery technology fields more particularly to a kind of battery of high safety and preparation method thereof.
Background technique
Lithium ion battery has many advantages, such as that energy density is high, charge lifetimes are long, is widely used in portable electronic product.So
And lithium ion battery such as overcharges, short circuit, high temperature under abuse conditions, can cause a series of side reaction, lead to thermal accumlation,
So that battery is in unsafe condition, and then cause safety accident, thus limits lithium ion battery in hybrid vehicle and electricity
The application of electrical automobile.
PTC (positive temperature coefficient) material, i.e., with the conductive heat-sensitive of positive temperature coefficient
Material, resistivity is within the scope of relatively narrow temperature, and as the temperature rises, the resistance of material can increase sharply.Existing lithium
Ion battery coats one layer of ptc material generally on positive and negative anodes tab, and contact area is small, and ptc material is generally placed in electricity
Outside pond, when lithium ion battery overcharge, short circuit or other reasons cause overheat, the heat of battery cannot be monitored in time and inhibited
It is out of control.Moreover, the Curie temperature of existing frequently-used ptc material is relatively high, generally between 130~170 DEG C, due to battery temperature
Many side reactions can occur at 130 DEG C for degree, thus the PTC Curie temperature of material need to be controlled at 130 DEG C hereinafter, additionally due to
The capacity of power battery will lead to PTC heating resistance when high current passes through PTC element and become larger generally in 40Ah~250Ah, and
PTC is not used also in power battery core at present.
Summary of the invention
In view of this, the battery has the purpose of the present invention is to provide battery of a kind of high safety and preparation method thereof
Higher safety.
The present invention provides a kind of batteries of high security, including battery core shell and the electricity for being located at the battery core interior of shell
Core；
The battery core is made by PTC pole piece, anode pole piece, diaphragm, cathode pole piece and electrolyte assembling；
The PTC pole piece includes collector A, PTC coating and collector B set gradually；
A tab is equipped on the anode pole piece, cathode pole piece, collector A and collector B；
The form of the assembling is lamination or winding；
PTC pole piece is placed in the first layer and/or the last layer of lamination；It is placed in the innermost layer of winding and/or outermost layer
PTC pole piece.
Preferably, the tab of multiple anode pole pieces forms anode ear group；The tab of multiple cathode pole pieces forms negative electrode lug group；
If placing one layer of PTC pole piece, the tab of any of the anode ear group and negative electrode lug group and any collector draws
It is used as cell polar ear out；The tab group not drawn is connected with the tab of another collector；
If placing two layers of PTC pole piece, anode ear group is connected with a tab of any PTC pole piece, negative electrode lug group with it is another
One tab of PTC pole piece is connected；Not connected PTC tab is drawn as cell polar ear；
Or two tabs of one layer of PTC pole piece are connected two-by-two with two tabs of another PTC pole piece, anode ear group and cathode
Any of ear group draws with PTC tab after any be connected as cell polar ear；The tab group not drawn with after another be connected
PTC tab is connected.
Preferably, the shape of the collector A and collector B is foil-like, continuous fine and close membranaceous, porous membranaceous or U-shaped film
Shape.
Preferably, the size of the PTC pole piece is less than or equal to the size of cathode pole piece；The size of the PTC pole piece is small
In or equal to anode pole piece size.
Preferably, the collector A with a thickness of 12~5000 μm；
The collector B with a thickness of 12~5000 μm；
The PTC coating with a thickness of 1~5000 μm.
Preferably, the transition temperature of the PTC coating is 50~150 DEG C.
Preferably, battery be lithium ion battery, lithium battery, solid state lithium battery, solid lithium ion battery, sode cell or sodium from
Sub- battery.
The present invention provides a kind of preparation methods of the battery of high safety described in above-mentioned technical proposal, comprising the following steps:
PTC slurry is coated in the single side of collector A carrier, PTC slurry is coated in the single side of collector B carrier, point
Collector A and collector B with PTC coating are not obtained；Respectively after prebake conditions, by the slurry coating of collector A and collector B
To patch, roll-in is dry, and cross cutting obtains PTC pole piece；If battery electrolyte is corrosive to PTC, one need to be added in PTC pole piece surrounding
Circle PP or PE is sealed against only electrolyte and immerses inside PTC pole piece, melts PE or PP by heat pressing process, makes collector
A and collector B bonding, to realize electrolyte and internal PTC layer isolation.
PTC pole piece, anode pole piece, diaphragm and cathode pole piece are assembled, battery core is made；The form of the assembling be lamination or
Winding；PTC pole piece is placed in the first layer and/or the last layer of lamination；PTC is placed in the innermost layer of winding and/or outermost layer
Pole piece；
Battery core is packaged, fluid injection, pre- chemical conversion, ageing, aging, partial volume, obtains the battery of high safety.
Preferably, the PTC slurry includes PTC material, conductive agent and binder；
The PTC material is selected from inorganic porous ceramic thermo-sensitive material and/or thermoplastic polymer；
Preferably, inorganic porous ceramic thermo-sensitive material includes barium titanate (BaTiO3), strontium titanates, Al2O3Ceramic powders, three
V 2 O (V2O3), the mixture of any one or more of the vanadium trioxide of doping or the barium titanate of doping, strontium titanates；
Thermoplastic polymer includes polyethylene, polypropylene, polymethyl methacrylate, plastic of poly vinyl acetate, polycaprolactone, poly- second
Alkene acetic acid, haloflex, polystyrene, oxidic polyethylene, hycar, acrylonitrile-butadiene-benzene second
Alkene copolymer, polyphenylene oxide, polycarbonate, polyvinyl chloride, tetrafluoraoethylene-hexafluoropropylene copolymer, polyamide, poly terephthalic acid
Glycol ester, polyphenylene sulfide, polyformaldehyde, phenolic resin, polyvinyl fluoride, polytetrafluoroethylene (PTFE), gathers polybutylene terephthalate (PBT)
Trifluoro-ethylene, maleic anhydride grafted polyethylene, polypropylene, Kynoar, epoxy resin, ethylene-vinyl acetate copolymer, second
One of alkene-acrylic copolymer is a variety of.
The conductive agent is selected from conductive black, superconduction carbon black, acetylene black, electrically conductive graphite, carbon nanotube, graphene, carbon fiber
One of peacekeeping conductivity ceramics powder is a variety of；
It is fine that the binder is selected from Kynoar, acrylic acid series copolymer, styrene-butadiene copolymer, methylol
It ties up in element, butadiene-styrene rubber, polyethylene glycol oxide, polyvinyl alcohol, polytetrafluoroethylene (PTFE), polyurethane, polypyrrole, polythiophene and polyaniline
It is one or more.
The present invention provides a kind of batteries of high security, including battery core shell and the electricity for being located at the battery core interior of shell
Core；The battery core is made by PTC pole piece, anode pole piece, diaphragm, cathode pole piece and electrolyte assembling；The PTC pole piece includes
Collector A, PTC coating and collector B set gradually；It is equal on the anode pole piece, cathode pole piece, collector A and collector B
Equipped with a tab, the form of the assembling is lamination or winding；The pole PTC is placed in the first layer and/or the last layer of lamination
Piece；Or PTC pole piece is placed in the innermost layer of winding and/or outermost layer, it can effectively prevent the thermal runaway of battery, have good anti-
It overcharges, over-discharge, the security features such as short circuit, improves the safety of battery.The battery structure is simple, easy to accomplish, it is easy to accomplish
Industrialization promotion.The present invention improves the safety of battery by the way that PTC pole piece is arranged in battery core.The results showed that with 5
A battery is test object, and when overcharging, battery core surface temperature is 40~52 DEG C；When short-circuit, battery core surface temperature is 30~64 DEG C；
Without flatulence；It is not on fire, it does not explode；Battery percent of pass is 4~5.
Detailed description of the invention
Fig. 1 is the tab of PTC pole piece provided by the invention in ipsilateral schematic diagram；
Fig. 2 is schematic diagram of the tab in two sides of PTC pole piece provided by the invention；
Fig. 3 is overcharged voltage-temperature profile of lithium battery prepared by embodiment 1；
Fig. 4 is overcharged voltage-temperature profile of lithium battery prepared by comparative example 1.
Specific embodiment
The present invention provides a kind of batteries of high security, including battery core shell and the electricity for being located at the battery core interior of shell
Core；
The battery core is made by PTC pole piece, anode pole piece, diaphragm, cathode pole piece and electrolyte assembling；
The PTC pole piece includes collector A, PTC coating and collector B set gradually；
A tab is equipped on the anode pole piece, cathode pole piece, collector A and collector B.
The present invention can effectively prevent the thermal runaway of battery, have good anti-mistake by the way that PTC pole piece is arranged in battery core
It fills, over-discharge, the security features such as short circuit, improves the safety of battery.The battery structure is simple, easy to accomplish, it is easy to accomplish work
Industryization is promoted.
The battery of high security provided by the invention includes battery core shell.The material of the battery core shell is metal or plastic-aluminum
Film.
The battery of high security provided by the invention includes the battery core for being located at the battery core interior of shell.The battery core passes through
PTC pole piece, anode pole piece, diaphragm, cathode pole piece and electrolyte assembling are made.
In the present invention, the battery core includes PTC pole piece；The PTC pole piece includes that collector A, the PTC set gradually is applied
Layer and collector B.Collector A, PTC coating and collector B are sandwich sandwich structure.PTC coating is by collector A and afflux
Body B physical isolation.PTC pole piece with sandwich structure, can increase the contact area of PTC, be effectively reduced and pass through PTC element
Current density, high current causes PTC pole piece to heat up, the problem of causing battery core resistance to become larger, simultaneously because PTC pole piece is placed on
The surface of battery core can perceive the temperature of battery core, when lithium ion battery overcharge, short circuit or other reasons cause overheat, the PTC
The resistance of pole piece, which steeply rises, to be haved the function that cut off electric current, to protect battery well；It, should after temperature is reduced to room temperature
The resistivity of ptc layer becomes smaller again, and battery still can work normally.
The material of the collector A and collector B is independently selected from copper, aluminium, nickel, copper nickel plating, carbon or stainless steel.Actually answer
In, the material of the collector A and collector B can be identical, can not also be identical.The shape of the collector A and collector B
Shape is foil-like, continuously fine and close membranaceous, porous membranaceous or U-shaped is membranaceous.In a particular embodiment, the collector A and collector B are only
On the spot it is selected from aluminium foil, copper foil, nickel foil, aluminium net, copper mesh or nickel screen.
A tab is equipped on the collector A and collector B；The tab of collector A and collector B on PTC pole piece
Tab can be in the same side, can also be in two sides.The tab of the collector A and the tab of collector B are greater than or equal to just
The tab of pole pole piece or the tab of cathode pole piece.Fig. 1 and Fig. 2 is participated in, Fig. 1 is the tab of PTC pole piece provided by the invention same
The schematic diagram of side；Fig. 2 is schematic diagram of the tab in two sides of PTC pole piece provided by the invention；Wherein, A is collector A；B is
PTC coating；C is collector B.
The size of the PTC pole piece is less than or equal to the size of cathode pole piece；The size of the PTC pole piece is less than or equal to
The size of anode pole piece.The size of the collector A and the size of collector B can be identical, can not also be identical.Specific real
It applies in example, the tab of the collector A and collector B are equal to positive and negative electrode pole-piece pole-ear；Or it is greater than positive and negative electrode pole-piece pole-ear.Institute
The thickness for stating collector A is preferably 12~5000 μm；More preferably 20~200 μm.The thickness of the collector B is preferably 12~
5000μm；More preferably 20~200 μm.
In the present invention, the form of the assembling is lamination or winding；
PTC pole piece is placed in the first layer and/or the last layer of lamination；It is placed in the innermost layer of winding and/or outermost layer
PTC pole piece.
In the present invention, the tab of multiple anode pole pieces forms anode ear group；The tab of multiple cathode pole pieces forms cathode
Ear group；
If placing one layer of PTC pole piece, the tab of any of the anode ear group and negative electrode lug group and any collector draws
It is used as cell polar ear out；The tab group not drawn is connected with the tab of another collector；
If placing two layers of PTC pole piece, anode ear group is connected with a tab of any PTC pole piece, negative electrode lug group with it is another
One tab of PTC pole piece is connected；Not connected PTC tab is drawn as cell polar ear.Or the tab of two PTC pole pieces
It is connected two-by-two, the tab of any of anode ear group and negative electrode lug group and PTC, which are drawn, is used as cell polar ear；The tab group not drawn
It is connected with the tab of another PTC.
In the present invention, the PTC coating is coated by PTC slurry and is made；The PTC slurry preferably includes positive temperature coefficient
Material, conductive agent and binder；In order to distinguish the conductive agent and binder in following technical proposals, what is used in PTC coating is led
Electric entitled first conductive agent of agent；The binder used in PTC coating is named as first binder.The PTC material,
First conductive agent and the mass ratio of first binder are preferably 10~85:5~80:0:20.The PTC coating by collector A and
Collector B physical isolation.The transition temperature of the PTC coating is preferably 50~150 DEG C, and more preferably 60~90 DEG C；Specific
In embodiment, the phase transition temperature of PTC coating is 70 DEG C.The thickness of PTC coating is preferably 1~5000 μm, more preferably 10~
500μm；In a particular embodiment, PTC coating with a thickness of 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm,
100 μm or 200 μm.
The PTC material is preferably selected from inorganic porous ceramic thermo-sensitive material and/or thermoplastic polymer；It is described
Inorganic porous ceramic thermo-sensitive material is preferably selected from barium titanate (BaTiO3), strontium titanates, Al2O3Ceramic powders, vanadium trioxide
(V2O3), the vanadium trioxide of doping, the barium titanate of doping and one of strontium titanates or a variety of.The thermoplastic polymer is excellent
Choosing is selected from polyethylene, polypropylene, polymethyl methacrylate, plastic of poly vinyl acetate, polycaprolactone, polyvinyl acetate, chlorine
Change polyethylene, polystyrene, oxidic polyethylene, hycar, acrylonitrile-butadiene-styrene copolymer,
Polyphenylene oxide, polycarbonate, polyvinyl chloride, tetrafluoraoethylene-hexafluoropropylene copolymer, polyamide, polyethylene terephthalate,
Polybutylene terephthalate (PBT), polyphenylene sulfide, polyformaldehyde, phenolic resin, polyvinyl fluoride, polytetrafluoroethylene (PTFE), poly- trifluoro-ethylene,
Maleic anhydride grafted polyethylene, polypropylene, Kynoar, epoxy resin, ethylene-vinyl acetate copolymer, ethylene-acrylic acid
One of copolymer is a variety of.In a particular embodiment, the PTC material is selected from polyvinyl acetate, gathers in oneself
One of ester, ethylene-vinyl acetate copolymer, polymethyl methacrylate and Kynoar are a variety of.
The conductive agent is preferably selected from conductive black, superconduction carbon black (Super P), acetylene black, electrically conductive graphite, carbon nanometer
One of pipe, graphene, carbon fiber and conductivity ceramics powder are a variety of；
The binder is preferably selected from Kynoar, acrylic acid series copolymer, styrene-butadiene copolymer, hydroxyl first
Base cellulose, butadiene-styrene rubber, polyethylene glycol oxide, polyvinyl alcohol, polytetrafluoroethylene (PTFE), polyurethane, polypyrrole, polythiophene and polyaniline
One of or it is a variety of.
It further include the first solvent in the PTC slurry；First solvent be preferably selected from N-Methyl pyrrolidone (NMP),
Petroleum ether, acetone, ethyl alcohol or water；It is more preferably selected from N-Methyl pyrrolidone.In the PTC slurry solid content be preferably 5~
20%.
In the present invention, the battery core includes anode pole piece, PTC pole piece, diaphragm, cathode pole piece and electrolyte；It is described just
The active main ingredient of pole pole piece is selected from ternary NCM and its modified material, ternary NCA and its modified material, cobalt acid lithium and its modified material
Material, LiFePO4 and its modified material or LiMn2O4 and its modified material.The anode pole piece prepare raw material it is also preferable to include
Second conductive agent, the second binder and the second solvent.In a particular embodiment, second conductive agent is superconduction carbon black；Second
Binder is PVDF；Second solvent is NMP.
The active main ingredient of the cathode pole piece be selected from graphite and its modified material, carbonaceous mesophase spherules and its modified material,
Silicon-carbon and its modified material, silicon oxygen carbon and its modified material or lithium titanate and its modified material.The preparation of the cathode pole piece is former
It is also preferable to include third conductive agent, third binder and third solvents for material.In embodiment, the active main ingredient of the cathode pole piece
Using graphite；Third conductive agent is superconduction carbon black；Third binder is CMC and SBR；Third solvent is water.
The present invention does not have special limitation to the electrolyte, using well known to those skilled in the art in battery
Electrolyte.If electrolyte is corrosive to PTC, a circle polypropylene or polyethylene need to be added to be sealed in PTC pole piece surrounding
To prevent electrolyte from immersing inside PTC pole piece.
In the present invention, battery be lithium ion battery, lithium battery, solid state lithium battery, solid lithium ion battery, sode cell or
Sodium-ion battery.
The present invention provides a kind of preparation methods of the battery of high safety described in above-mentioned technical proposal, comprising the following steps:
PTC slurry is coated in the single side of collector A carrier, PTC slurry is coated in the single side of collector B carrier, point
Collector A and collector B with PTC coating are not obtained；Respectively after prebake conditions, by the slurry coating of collector A and collector B
To patch, roll-in is dry, and cross cutting obtains PTC pole piece；If battery electrolyte is corrosive to PTC, one need to be added in PTC pole piece surrounding
Circle PP or PE is sealed against only electrolyte and immerses inside PTC pole piece.
PTC pole piece, anode pole piece, diaphragm, cathode pole piece and electrolyte are assembled, battery core is made；The form of the assembling is
Lamination or winding；PTC pole piece is placed in the first layer and/or the last layer of lamination；Or innermost layer and/or outermost layer in winding
Place PTC pole piece；
Battery core is packaged, fluid injection, pre- chemical conversion, ageing, aging, partial volume, obtains the battery of high safety.
PTC slurry is coated in the single side of collector A carrier by the present invention, and PTC slurry is coated in the list of collector B carrier
Face respectively obtains collector A and collector B with PTC coating；Respectively after prebake conditions, by the slurry of collector A and collector B
Coating is expected to patch, and roll-in is dry, and cross cutting obtains PTC pole piece.The raw material and material content of the PTC slurry and above-mentioned technical side
Consistent described in case, details are not described herein.The present invention preferably mixes binder with solvent, then is separately added into PTC material
It is uniformly mixed with conductive agent, obtains PTC slurry.PTC slurry is preferably coated in collector A with the speed of 1~3m/s by the present invention
On carrier, collector A is obtained；More preferably 2m/s.PTC slurry is preferably coated in afflux with the speed of 1~3m/s by the present invention
On body B carrier, collector B is obtained；More preferably 2m/s.The present invention prebake conditions collector A and afflux preferably at 40~90 DEG C
Body B.The present invention preferably by the slurry coating of collector A and collector B to patch, after roll-in 40~90 DEG C dry 12~for 24 hours.Mould
When cutting, the tab of PTC pole piece can be in the same side, can also be in two sides.
PTC pole piece, anode pole piece, diaphragm, cathode pole piece and electrolyte are assembled, battery core is made；The form of the assembling is
Lamination or winding；PTC pole piece is placed in the first layer and/or the last layer of lamination；It is put in the innermost layer of winding and/or outermost layer
Set PTC pole piece.
After obtaining battery core, battery core is packaged by the present invention, fluid injection, pre- chemical conversion, ageing, aging, partial volume, obtains high safety
Battery.The present invention is not particularly limited the method for encapsulation, fluid injection, pre- chemical conversion, ageing, aging, partial volume, using this field skill
Encapsulation known to art personnel, fluid injection, pre- chemical conversion, ageing, aging, partial volume technical solution.
In order to further illustrate the present invention, below with reference to embodiment to a kind of battery of high safety provided by the invention and its
Preparation method is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Examples 1 to 10
1 PTC foil of table
| Foil 1 | Aluminium foil |
| Foil 2 | Copper foil |
| Foil 3 | Nickel foil |
| Foil 4 | Aluminium net |
| Foil 5 | Copper mesh |
| Foil 6 | Nickel screen |
2 PTC pole-piece pole-ear of table
| The tab of PTC collector A, B | PTC collector A, B tab position | |
| Tab 1 | Equal to positive and negative anodes pole-piece pole-ear | It is ipsilateral |
| Tab 2 | Greater than positive and negative anodes pole-piece pole-ear | It is ipsilateral |
| Tab 3 | Equal to positive and negative anodes pole-piece pole-ear | Two sides |
| Tab 4 | Greater than positive and negative anodes pole-piece pole-ear | Two sides |
3 PTC slurry of table
| PTC slurry | PTC material | Conductive agent | Solvent |
| Slurry 1 | Polyvinyl acetate | Superconduction carbon black | Ethyl alcohol |
| Slurry 2 | Polycaprolactone | Superconduction carbon black | N-Methyl pyrrolidone |
| Slurry 3 | Ethylene-vinyl acetate copolymer | Superconduction carbon black | Petroleum ether |
| Slurry 4 | Polymethyl methacrylate | Superconduction carbon black | N-Methyl pyrrolidone |
| Slurry 5 | Polymethyl methacrylate, Kynoar | Superconduction carbon black | N-Methyl pyrrolidone |
4 PTC pole piece of table
The lithium ion battery of 5 high security of table
| PTC pole piece | Battery core manufacture craft | PTC pole piece position | |
| Embodiment 1 | Pole piece 1 | Lamination | The first layer of lamination |
| Embodiment 2 | Pole piece 2 | Lamination | The last layer of lamination |
| Embodiment 3 | Pole piece 3 | Lamination | The first layer and the last layer of lamination |
| Embodiment 4 | Pole piece 4 | Winding | The innermost layer of winding |
| Embodiment 5 | Pole piece 5 | Winding | The outermost layer of winding |
| Embodiment 6 | Pole piece 6 | Winding | The innermost layer of winding and outermost layer |
| Embodiment 7 | Pole piece 7 | Lamination | The first layer and the last layer of lamination |
| Embodiment 8 | Pole piece 8 | Winding | The outermost layer of winding |
| Embodiment 9 | Pole piece 9 | Lamination | The first layer of lamination |
| Embodiment 10 | Pole piece 10 | Lamination | The last layer of lamination |
The preparation of PTC pole piece
The preparation of a.PVAc (polyvinyl acetate) base PTC pole piece
Polyvinyl acetate and ethyl alcohol are stirred at 50~80 DEG C to it completely according to mass percent 10~50:90~50
Dissolution, then addition SP, which is uniformly mixed, obtains PTC slurry 1.Obtained PTC slurry is coated in 2m/s speed with a thickness of 20 μm
Collector A carrier and collector B carrier on, control surface density, make after drying 10 μm of coating thickness of precoated shet, set
In 80 DEG C of prebake conditions 2h；By the roasted PTC pole piece alignment of two panels preliminary drying, by way of roll-in, by two panels single side coating PTC's
Pole piece is close together, and wherein collector A is identical as collector B size, and the PTC pole piece Jing Guo roll-in is continued in 80 DEG C of baking ovens
Dry 12h；Then cross cutting obtains the PTC pole piece with sandwich structure, tests its PTC transition temperature.
If battery electrolyte is corrosive to PTC, circle a PP or PE need to be added to be sealed against only in PTC pole piece surrounding
Electrolyte immerses inside PTC pole piece.
The preparation of b.PCL (polycaprolactone) base PTC pole piece
PCL base PTC pole piece preparation method is similar with PVAc base stage piece, the difference is that, matrix polyvinyl acetate is changed
At polycaprolactone, solvent changes ethyl alcohol into NMP, remaining step is same as above.
The preparation of c.EVA (ethylene and vinyl acetate copolymer) base PTC pole piece
Petroleum ether, EVA, PEO, Super P are condensed at 100 DEG C according to 30: 35: 25:10 mass percent of mass ratio
Reflux 5h obtains uniformly mixed PTC slurry 2, remaining step is same as above.
The preparation of d.PMMA (polymethyl methacrylate) base PTC pole piece
PMMA base PTC pole piece preparation method is similar with PVAc base stage piece, the difference is that, matrix polyvinyl acetate is changed
At polymethyl methacrylate, solvent changes ethyl alcohol into NMP, remaining step is same as above.
The preparation of e.PMMA-PVDF base PTC pole piece
The preparation method of PMMA-PVDF base PTC pole piece is similar with PVAc base stage piece, the difference is that, by the poly- second of matrix
Alkene acetic acid changes PMMA and PVDF solvent into respectively and changes ethyl alcohol into NMP.
The preparation of the lithium ion battery of high safety:
Positive electrode active materials are using ternary active substance, and conductive agent is Super P, binder PVDF, and solvent is
It is uniformly mixed according to a certain percentage and obtains positive electrode active materials slurry, and is coated on aluminium foil by NMP, and drying obtains
Positive plate.
Negative electrode active major ingredient uses graphite, and conductive agent is Super P, and binder is CMC and SBR, and solvent is water, is pressed
It is uniformly mixed according to certain proportion and obtains negative active material slurry, and it is coated on copper foil, drying obtains negative electrode tab.
By above-mentioned obtained positive plate, negative electrode tab and PTC pole piece with sandwich structure, using lamination process, by lamination
First layer place PTC pole piece, wind by diaphragm and prepares battery core, the afflux of the pole-piece pole-ear of battery core and PTC pole piece
Body tab links together, another tab of PTC pole piece and the tab of battery core are connected；It is pre- through subsequent encapsulation, fluid injection, high temperature again
The lithium-ion electric of high security is made in the processes such as chemical conversion, high temperature ageing, room temperature aging, partial volume.
Comparative example 1
Positive plate obtained above, negative electrode tab by subsequent film-making, assembly, fluid injection, activation process obtain that Sanming City is not added
Control the lithium ion battery of the PTC pole piece of structure.
By lithium ion battery made from Examples 1 to 10 and comparative example 1 according to lithium ion battery GB-T31485-2015
Power accumulator safety requirements for electric vehicle and test method carry out safety test, and main includes overcharging test and short circuit to survey
Examination.
Overcharge test: battery is according to 1C constant-current constant-voltage charging, cut-off current 0.05C；Again to battery with 1C constant-current charge extremely
1.5~2 times of battery voltage rating；1h is observed, the variation of battery core surface temperature during this is monitored, and records whether battery core rises
It is hot fried.
Short-circuit test: battery is according to 1C constant-current constant-voltage charging, cut-off current 0.05C；Again with outside line internal resistance < 5m Ω
Conducting wire connects battery core positive and negative anodes, short circuit duration 10min；1h is observed, monitors the temperature on this process battery core surface, and record battery core to be
It is no on fire, explosion.
It overcharges as follows with short-circuit test result:
Battery prepared by 6 Examples 1 to 10 of table and comparative example 1 overcharges test result
| Overcharge test | Battery core surface temperature/DEG C | Battery whether flatulence | Whether battery is on fire, explodes | Battery percent of pass |
| Comparative example | 128 | It is | It is on fire, do not explode | 0/5 |
| Embodiment 1 | 40 | It is no | It is no | 5/5 |
| Embodiment 2 | 45 | It is no | It is no | 5/5 |
| Embodiment 3 | 39 | It is no | It is no | 4/5 |
| Embodiment 4 | 46 | It is no | It is no | 5/5 |
| Embodiment 5 | 37 | It is no | It is no | 5/5 |
| Embodiment 6 | 52 | It is no | It is no | 4/5 |
| Embodiment 7 | 50 | It is no | It is no | 5/5 |
| Embodiment 8 | 43 | It is no | It is no | 5/5 |
| Embodiment 9 | 40 | It is no | It is no | 5/5 |
| Embodiment 10 | 44 | It is no | It is no | 5/5 |
The short-circuit test result of battery prepared by 7 Examples 1 to 10 of table and comparative example 1
Fig. 3 is overcharged voltage-temperature profile of lithium battery prepared by embodiment 1；Fig. 4 is lithium electricity prepared by comparative example 1
Overcharged voltage-the temperature profile in pond.As can be seen from figs. 3 and 4: when having PTC protection, with the raising of voltage, temperature slowly increases
Add, when reaching the transition temperature of PTC, since resistance sharply increases, temperature increase is slower, and the heat of battery can be inhibited to lose
Control.When no PTC is protected, when battery is in overcharging state, cathode de- lithium current potential increases with the degree that overcharges and is risen rapidly, and exceeds
After the electrochemical window of electrolyte, irreversible oxygenolysis will occur for electrolyte, generate combustible gas gas and discharge a large amount of
Heat, cause battery temperature and internal pressure to sharply increase.So PTC can be effectively improved the overcharge safety of battery.
As seen from the above embodiment, the present invention provides a kind of battery of high security, including battery core shell and it is located at institute
State the battery core of battery core interior of shell；The battery core passes through PTC pole piece, anode pole piece, diaphragm, cathode pole piece and electrolyte assembling system
?；The PTC pole piece includes collector A, PTC coating and collector B set gradually；The anode pole piece, cathode pole piece, collection
The form that assembling described in a tab is equipped on fluid A and collector B is lamination or winding；Lamination first layer and/or
The last layer places PTC pole piece；PTC pole piece is placed in the innermost layer of winding and/or outermost layer.The present invention in battery core by setting
PTC pole piece is set, the safety of battery is improved.The results showed that using 5 batteries as test object, when overcharging, battery core surface
Temperature is 40~52 DEG C；When short-circuit, battery core surface temperature is 30~64 DEG C；Without flatulence；It is not on fire, it does not explode；Battery is logical
Crossing rate is 4~5.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of battery of high security, including battery core shell and the battery core for being located at the battery core interior of shell；
The battery core is made by PTC pole piece, anode pole piece, diaphragm, cathode pole piece and electrolyte assembling；
The PTC pole piece includes collector A, PTC coating and collector B set gradually；
A tab is equipped on the anode pole piece, cathode pole piece, collector A and collector B；Collector A's and collector B
Tab can be in the same side or two sides；
The form of the assembling is lamination or winding；
PTC pole piece is placed in the first layer and/or the last layer of lamination；
Or PTC pole piece is placed in the innermost layer of winding and/or outermost layer.
2. battery according to claim 1, which is characterized in that the tab of multiple anode pole pieces forms anode ear group；It is multiple
The tab of cathode pole piece forms negative electrode lug group；
If placing one layer of PTC pole piece, the tab of any of the anode ear group and negative electrode lug group and any collector, which is drawn, to be made
For cell polar ear；The tab group not drawn is connected with the tab of another collector；
If placing two layers of PTC pole piece, anode ear group is connected with a tab of any PTC pole piece, negative electrode lug group and another pole PTC
One tab of piece is connected；Not connected PTC tab is drawn as cell polar ear；
Or two tabs of one layer of PTC pole piece are connected two-by-two with two tabs of another PTC pole piece, anode ear group and negative electrode lug group
Any of draw with PTC tab after any be connected as cell polar ear；The tab group not drawn and the pole PTC after another be connected
Ear is connected.
3. battery according to claim 1, which is characterized in that the material of the collector A and collector B independently selected from
Copper, aluminium, nickel, copper nickel plating, carbon or stainless steel.
4. battery according to claim 1, which is characterized in that the shape of the collector A and collector B is foil-like, connects
Continuous fine and close membranaceous, porous membranaceous or U-shaped is membranaceous.
5. battery according to claim 1, which is characterized in that the size of the PTC pole piece is less than or equal to cathode pole piece
Size；The size of the PTC pole piece is less than or equal to the size of anode pole piece.
6. lithium ion battery according to claim 1, which is characterized in that the tab of collector A or collector B be greater than etc.
In positive and negative anodes pole-piece pole-ear；The collector A with a thickness of 12~5000 μm；
The collector B with a thickness of 12~5000 μm；
The PTC coating with a thickness of 1~5000 μm.
7. battery according to claim 1, which is characterized in that the transition temperature of the PTC coating is 50~150 DEG C.
8. battery according to claim 1, which is characterized in that battery be lithium ion battery, lithium battery, solid state lithium battery,
Solid lithium ion battery, sode cell or sodium-ion battery.
9. a kind of preparation method of the battery of any one of claim 1~8 high safety, comprising the following steps:
PTC slurry is coated in the single side of collector A carrier, PTC slurry is coated in the single side of collector B carrier, respectively
To the collector A and collector B for having PTC coating；Respectively after prebake conditions, by the slurry coating pair of collector A and collector B
Patch, roll-in is dry, and cross cutting obtains PTC pole piece；
PTC pole piece, anode pole piece, diaphragm and cathode pole piece are assembled, battery core is made；The form of the assembling is lamination or winding；
PTC pole piece is placed in the first layer and/or the last layer of lamination；Or the pole PTC is placed in the innermost layer of winding and/or outermost layer
Piece；
Battery core is packaged, fluid injection, pre- chemical conversion, ageing, aging, partial volume, obtains the battery of high safety.
10. preparation method according to claim 9, which is characterized in that the PTC slurry include PTC material,
Conductive agent and binder；
The PTC material is selected from inorganic porous ceramic thermo-sensitive material and/or thermoplastic polymer；
The conductive agent be selected from conductive black, superconduction carbon black, acetylene black, electrically conductive graphite, carbon nanotube, graphene, carbon fiber and
One of conductivity ceramics powder is a variety of；
The binder be selected from Kynoar, acrylic acid series copolymer, styrene-butadiene copolymer, hydroxymethyl cellulose,
One of butadiene-styrene rubber, polyethylene glycol oxide, polyvinyl alcohol, polytetrafluoroethylene (PTFE), polyurethane, polypyrrole, polythiophene and polyaniline
Or it is a variety of.
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| CN110783619A (en) * | 2019-11-20 | 2020-02-11 | 北京卫蓝新能源科技有限公司 | Lithium battery with self-heating function and preparation method thereof |
| CN110931710A (en) * | 2019-12-16 | 2020-03-27 | 东莞维科电池有限公司 | Positive electrode substrate, preparation method and application thereof |
| CN111509181A (en) * | 2020-04-20 | 2020-08-07 | 海口博澳国兴新能源科技有限公司 | Battery tab and preparation method thereof |
| CN114709423A (en) * | 2022-03-30 | 2022-07-05 | 清华大学 | Composite current collector, battery cell structure and lithium ion battery |
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Effective date of registration: 20221222 Address after: 102402 No. 1, Qihang West Street, Doudian Town, Fangshan District, Beijing Patentee after: BEIJING WELION NEW ENERGY TECHNOLOGY Co.,Ltd. Patentee after: INSTITUTE OF PHYSICS, CHINESE ACADEMY OF SCIENCES Address before: 102402 No.1, Qihang West Street, Doudian Town, Fangshan District, Beijing Patentee before: BEIJING WELION NEW ENERGY TECHNOLOGY Co.,Ltd. |